THE TRANS INFLUENCE IN [RH(PH3)3CL] - A DENSITY-FUNCTIONAL THEORY STUDY
被引:12
作者:
DEETH, RJ
论文数: 0引用数: 0
h-index: 0
DEETH, RJ
机构:
来源:
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
|
1993年
/
24期
关键词:
D O I:
10.1039/dt9930003711
中图分类号:
O61 [无机化学];
学科分类号:
070301 ;
081704 ;
摘要:
Optimised geometries computed using the local density approximation (LDA) of density functional theory (DFT) have been obtained for the Wilkinson's catalyst model complex [Rh(PH3)3Cl]. The LDA method accurately predicts the 0.09 angstrom shortening of the Rh-P(trans) distance relative to Rh-P(cis) although the Rh-Cl contact is about 0.05 angstrom too short. These geometrical data are significantly better than single determinant Hartree-Fock (HF) results. In contrast, the Mulliken charge density analyses are very similar and give comparable descriptions of the bonding although small differences in the predicted d-orbital sequences suggest that the LDA method describes a stronger in-plane pi-acceptor interaction than does HF theory.